N-{107 -cyano-alkyl)-carbamyl benzimidazoles used as insecticides, acaricides and ovicides

ABSTRACT

Insecticidal, acaricidal and ovicidal compositions containing as active ingredients N-( omega -cyano-alkyl)-carbamylbenzimidazoles of the tautomeric formulae (I):   and   IN WHICH R is hydrogen, alkoxycarbonyl having 2-5 carbon atoms or alkylcarbonyl having 1-5 carbon atoms, R&#39;&#39; is hydrogen or alkyl of 1-4 carbon atoms, and x is a whole number from 1 to 11.

Daum et Feb. 4, 1975 N-(m-CYANO-ALKYLJ CARBAMYL BENZIMIDAZOLES USED AS INSECTICIDES, ACARICIDES AND OVICIDES [75] Inventors: Werner Daum, Krefeld-Bockum;

Hans Scheinpflug; Paul-Ernst Frohberger, both of Leverkusen; Ferdinand Greene, Burscheid, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Aug. 29, 1973 [21] Appl. No.: 392,833

, Related US. Application Data [62] Division of Ser. No. 206,180, Dec. 8, 1971, Pat. No. 3,794,728, which is a division of Ser. No. 880,399, Nov. 26, 1969, Pat. No. 3,673,210.

[30] Foreign Application Priority Data Nov. 30, 1968 Germany 1812000 [52] US. Cl. 424/273 [51] 1nt.Cl A0ln 9/22 [58] Field of Search 424/273; 260/309.2

[56] References Cited UNITED STATES PATENTS 3,336,191 8/1967 Craig et a1. 260/3092 3,399,212 8/1968 Hoover et a1... 260/3092 3,541,213 11/1970 Klopping 260/3092 3,673,210 6/1972 Daum et a1. 260/3092 Primary Examiner-Albert T. Meyers Assistant Examiner-Leonard Schenkman Attorney, Agent, or FirmBurgess', Dinklage & Sprung [57] ABSTRACT Insecticidal, acaricidal and ovicidal compositions containing as active ingredients N-(w-cyano-alkyll-cnrbamyl-benzimidazoles of the tautomeric formulae (1):

in which R is hydrogen, alkoxycarbonyl having 2-5 carbon atoms or alkylcarbonyl having 1-5 carbon atoms, R is hydrogen or alkyl of l-4 carbon atoms, and x is a whole number from 1 to 11.

11 Claims, No Drawings 1 N-(a) -CYANO- ALKYL):CARBAMYL BENzIK'IIDAZGLES USED AS INSECTICIDES,

ACARICIDES AND OVICIDES This is a division of application Ser. No. 206,180, filed Dec. 8, 1971, now US. Pat. No. 3,794,728, issued Feb. 26, 1974, which in turn is a division of application Ser. No. 880,399, filed Nov. 26, 1969-, now US. Pat. No. 3,673,210, issued June 27, 1973.

The present invention relates to and has for its objects the use of new N-(w-cyano-alkyl)'carbamylbenzimidazoles, i.e. 2-(optionally alkoxy-carbonyl and alkyl-carbonyl 3-[ N-( w-cyano-alkyl l-carbamyl ]-4,5,6 and/r 7-(opti0nally alkyU-benzimidazoles, which possess fungicidal, anti-bacterial, insecticidal, acaricidal and ovicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating fungi, bacteria, arthropods, e.g. insects and acarids, and the corresponding arthropod egg stages, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that trichloromethylmercapto compounds, particularly N-trichloromethylthio-tetrahydrophthalimide (A), can be used as fungicidally active compounds (cf. German Pat. No. 921,290).

It has now been found, in accordance with the present invention, that the particular new N-(w-cyanoalkyl)-carbamyl-benzimidazoles of the tautomeric formulae (l):

' process which comprises 1 a. reacting a benzimidazole of the formula:

in which R and R are the same as defined above, with a cyanoalkyl-isocyanate of the formula:

OCN-(CHgh'CN (III) in which x is the same as defined above,

'b. reacting a benzimidazole of formula (II) above with a cyanoalkyI-carbamic acid chloride of the formula:

CI-CO-NH'(CH2):'CN

in which x is the same as defined above,

c. reacting a benzimidazole of formula (11) above 7 with phosgene and then reacting the resulting chloroformyl-benzimidazole of the formula:

00-01 R CNHR N in which R and R are the same as defined above, with a cyanoalkyl amine of the formula:

in which x is the same as defined above. Surprisingly, the active compounds of formula (1) above according to the present invention show a higher 'Advantageously, in accordance with the present in-- .vention, in the various formulae herein:

0 alkoxy-dlor carbo-C a1koxy, especially 02.,

O or C alkoxycarbonyl, Le. O or 01-1 alkoxy-l1;

or alkylcarbonyl, i.e. alkanoyl, having 1-5 carbon atoms such as foi'myl, and methyl, ethyl, nand lsopropy1, 11-, is0, sec.- and tert.-butyl, and

O the like, carbonyl, La. formyl and C a1kyl-i or 01-5 alkanoyl, especially Cz-n or 62-4 or Cg-n alkylcarbonyl, i.e. CH or 01-2 alkyI--fi R represents hydrogen; v

of 1-4 carbon atoms such as methyl, ethyl, nand isopropyl, n-, iso-, sec.- and tert.-butyl, and the like, i.e. in 4-, 5-, 6- or 7- nuclear position of the benzo moiety, especially C or C alkyl, more especially 5- and 7- nuclear position C or C alkyl, and most especially 5- and 7- nuclear position methyl; and

x represents a whole number from 1-11, i.e. from 1 or 2 or 3 or 4 or 5 up to 11, especially 5-11.

Preferably, R is hydrogen; or C alkoxycarbonyl, i.e. carbo-C alkoxy; or C alkylcarbonyl, i.e. C alkanoyl; R is hydrogen; or C alkyl; and x is a whole number from 5-11.

In particular, R is hydrogen; or C alkoxycarbonyl, i.e. carbo-C alkoxy; or C alkylcarbonyl, i.e. C alkanoyl; R is hydrogen; or methyl, such as 5- and 7- methyl; and x is 5-11.

If N-(benzimidazol-Z-yl)-carbamic acid ethyl ester and w-isocyanato-caproic acid nitrile are used according to process variant (a) as starting materials, the reaction course is represented by the following formula scheme:

v 1) In process variant (b), the corresponding reaction course, with the splitting off of HCI, is represented by the following formula scheme:

00-01 o-Nu-co-o-cgus (Va) (Via) The starting materials which may be used are clearly characterized by formulae (11), (111). (IV) and (VI) above. with formula (V) designating an appropriate intermediate.

A list ofexamples ofthe benzimidazole starting materials of formula (11) above which may be reacted includes:

Z-amino-benzimidazole;

4-methyl, 4-ethyl, 4-n-propyl, 4-iso-propyl-. 4-n-.

butyl-, 4-isobutyl-, 4-sec.-butyl-. 4-tert.-butyl-, and the like, -2-amino-benzimidazole; 5-methyl-, 5-ethyl-, 5-npropyl, 5-isopropyl-, -5-n-butyl-, 5-isobutyl-, 5-sec.- butyl-, 5-tert.-butyl-, and the like. -2-aminobenzimidazole;

N-(benzimidazol-Z-yl)-carbamic acid methyl ester. -ethyl ester, -propyl ester, -iso-propyl ester, -n-buty1 ester, -iso-butyl ester, -sec.-butyl ester, tert.-butyl ester, and the like;

2-(.formyl-amin0)-, 2-(acety1-amino)-, Z-(propionylamino)-, 2-(butanoyl-amino)-, 2-(isobutanoyl-amino)-, and the'like, benzimidazole;

N-(4- or 5-methyl-, 4- or 5-ethyl-, 4- or 5-n-propyl-, 4- or 5-isopropyl-, 4- or 5-n-butyl-, 4- or 5-isobutyl-, 4- or 5-sec.-buty1-, 4- or 5-tert.-butyl, and the like, benzimidzizol-Z-yl)-carbamic acid methyl, -ethyl, -npropyl, -isopropyl, -n-butyl, -isobutyl, -sec.-butyl, -tert.- butyl ester, and the like; and

N-(4- or 5-methyl, 4- or S-ethyl, 4- or 5-propy1-, 4- or 5-isopro'py l, 4- or S-n-butyl- 4- or 5-isobutyl-, 4- or -5-sec.-butyl-, 4- or 5-tert.-butyl, and the like, benzimidazol-2-yl)- -amide, or -carbamoyl-methane, -ethane, -propane, -isopropane, -n-butane, -isobutane, -sec.-butane, and -tert.-butane; and the like.

A list of examples of the isocyanate, carbamic acid chloride and amine starting materials of formulae (1"), (1V) and (VI) above, respectively, which may be reacted includes:

w-cyano-methy1-, w-cyano-ethyh, w-cyano-propyl-, w-cyano-butylw-cyano-pentyl-, w-cyano-hexyl, w-cyano-heptyl-, w-cyano-octyl-, wcyano-nonyl-, w-cyano-decyland w-cyano-undecyl, -iso-cyanate, -carbamic acid chloride, and -amine, and the like.

The'various starting materials are for the most part known [compare J. Am. Chem. Soc. 56, 144-6, 1934, US. Pat. Nos. 2,933,502, 2,933,504; and 3,010,968; Belgian Pat. No. 691 611; Ann. 562, -136, (1949); and Ber. 89, 2677-81, (1956)],

Those starting materials which are still new can be obtained correspondingly according to the appropriate known processes.

Reaction variant (a) is expediently carried out in an inert organic solvent, such as dimethyl sulfoxide, di-

methyl formamide, dimethyl acetamide, acetone. diethyl ketone, methylene chloride, chloroform, 1,2- dichloro-ethane, chlorobenzene, toluene, acetonitrile, benzonitrile, ethyl acetate, and the like. Such reaction variant (a) is generally carried out at a temperature with the range of substantially between about -l0 to +60C, and preferably between about -40C. For variant (a), in this regard, tertiary amines. such as triethyl amine, dimethyl aniline. pyridine, picoline, and the like, may be present as reaction accelerators. It is also possible to carry out the reaction in a tertiary amine as diluent or solvent, or when 2-aminobenzimidazole starting materials of formula (ll) above are used, in which R represents alkoxycarbonyl or alkylcarbonyl, to carry out the reaction in excess cyanoalkyl-isocyanate of formula (III) above as diluent or solvent.

ln carrying out reaction variant (b), the w-cyanoalkyl-carbamic acid chloride of formula (W) above may be added to a mixture consisting of the Z-aminobenzimidazole starting material of formula (ll) above, and an inert organic solvent of the type specified above in connection with reaction variant (a) or, for example, a tertiary amine, such as triethyl amine, dimethylbenzyl amine, diethyl aniline, pyridine, picoline, quinoline, and the like, or an alkaline-reacting substance, such as potassium carbonate, sodium carbonate, borax, trilithium phosphate, and the like. It is also possible in connection with reaction variant (b) to add the w-cyanoalkyl-carbamic acid chloride of formula (W) above to a mixture consisting of the Z-aminobenzimidazole starting material of formula (II) above and an inert, water-immiscible organic solvent and water as well as an acid acceptor, i'.e. acid binding agent, ofthe usual type such as a tertiary amine or solution of alkali or solution of alkali metal carbonate. The

reaction temperatures for variant (b) are preferably from substantially between l0 to +l0C.

ln carrying out reaction variant (c), the substituted Z-amino-benzimidazole starting material of formula (ll) above, preferably in the form of the monohydrochloride, may be treated with phosgene at substantially between about 40 to +20C, and preferably at between about -20 to 0C, in an inert organic solvent, such as acetonitrile, benzonitrile, acetone, methylethyl ketone, benzene, chlorobenzene, methylene chloride, ethylene chloride, and the like, and an equimolar amount of a tertiary amine, such as dimethyl aniline, diethyl aniline, pyridine, picoline, quinoline, and the like, may then be added as acid binding agent. After the excess phosgene has been distilled off (this is advantageously done in a vacuum) or after treatment of the reaction mixture with water, reaction of the intermediately formed chloroformylbenzimidazole of formula (V) above with the w-cyano-alkylamine of formula (VI) above may be effected. according to variant (c); in the presence of the stoichiometric amount of a tertiary amine, or the like, as acid binding agent. It is also possible first to add to the two-phase reaction mixture consisting of water and an inert, water immiscible solvent the 'w'cyano-alkyl-amine to be reacted according to variant (0) and then the necessary amount of a tertiary amine, aqueous solution of alkali or solution or' alkali metal carbonate, or the like, or to use excess w-cyano-alkylamine, for the binding of the hydrogen chloride which forms. The reaction temperatures for variant (c) are generally substantially between about to +C, and preferably between about -3 to +l0C.

The particular new compounds according to the present invention may be present in a tautomeric equilibrium corresponding to both formula (l) and formula (l") above. as the artisan will appreciate. For reasons of simplicity, the corresponding specific formulae according to the tautomeric limiting state of formula (l") above are not shown in each appropriate instance herein, yet it will be realized that for the purposes of the present invention, the stated specific formulae corresponding to the tautomeric limiting state of formula (I') above are deemed herein in each individual case to comprise the corresponding formulae according to the tautomeric limiting state of formula (l") herein just as if such corresponding formula (l") were set forth specifically in each appropriate instance.

Advantageously, the active compounds according to the present invention exhibit strong fungitoxic and antibacterial activity and are distinguished by a broad spectrum of activity. In the concentrations necessary for the control of fungi and bacteria, the instant active compounds do not damage cultivated plants, and also have a low toxicity to warm-blooded animals. For these reasons, such active compounds are suitable for use as crop protection agents for the control of fungi and bacteria.

Fungitoxic agents in crop protection, such as the instant compounds, are used, for example, for the control of fungi from the most diverse classes including Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfecti.

The active compounds according to the present invention have a very broad spectrum of activity, as aforesaid, and can be applied against parasitic fungi and bacteria which infest above-the-soil parts of plants or attack the plants from the soil, as well as seed-borne pathogenic agents.

In particular, the active compounds according to the present invention act specifically against numerous plant-pathogenic fungi which infest cultivated plants, such as Cochliobolus miyabeunus, Myt'osphaerella musicola, Cerc'uspora personara, Butryt is cinerea and Alternaria species, Venturia species (causative organisms of apple scab and pear scab), Phytoplirhora infesrans, Plamopara viticolu, and the like. In addition, such compounds show a very distinct activity against powdery mildew fungi, such as Podosp/raera leucotriclra (powdery mildew of apples) and Erysiphe polyp/raga (powdery mildew of cucumbers). Surprisingly, the instant active compounds have not only a protective action but also a curative and systemic effect.

Significantly, the active compounds according to the present invention show an excellent activity against the fungi Pirit'uluria oryzae and Pellicularia sasakii, by reason of which they can be used for the joint control of these two rice diseases. This joint control represents a substantial advance. since, up to now, agents of different chemical constitution were individually necessary to combat'these two fungi.

The instant active compounds are likewise highly effective and of special practical importance when they are used as seed dressings or soil treatment agents against phytopathogenic fungi which adhere to the seed or occur in the soil and cause, in cultivated plants, diseases of seedlings, root-rots, tracheomycoses, stem, blade, leaf, blossom, fruit or seed diseases, such as Tilletia caries, Hehninr/wsporium gramineum, Fusarium nivale, F usarium culmurum, Rliizut'mnia .rulani, Phialophora cinerescens, Verlicillium alboatrum, Fusarium diam/ii, Fusarium cubense, Fusarium oxysporum, Fu-

sarium solam', Sclerolinia sc/tlemtiorum, 'IIu'elaviopsis basicala, Phytuphthora cacturum. and the like.

As examples of bacteria which can be controlled in accordance with the present invention, there may be mentioned: Xanrhomonas oryzae, Pseudomonas luclzrymans, and the like.

Significantly, the instant active compounds also show an insecticidal, acaricidal and ovicidal activity and can therefore be used for the control of noxious sucking and biting insects, Diptera and mites (Acarina), such as M yzus persicae, PIureI/a maculipennis', Drosop/rilu melanogaster, Telranychus urticae, and the like. The active compounds are particularly effective against the corresponding egg stages.

The active compounds according to the instant invention can be utilized, if desired in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles, such as solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules etc. These are prepared in known 'manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersinging agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g.

chlorobenzenes, etc.), paraffins (e.g. petroleum frac-.

tions), chlorinated aliphatic hydrocarbons (e,g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, etheralcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide,etc.), ketones (e.g. acetone, etc.), and/or water; as well asinert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional car-' rier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium steain the form of particular dosage preparations for specific application made therefrom, such as solutions,

emulsions, suspensions, powders, pastes, and granules which are thus ready for use. 7 5 As concerns commercially marketed preparations.

these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95 percent. and preferably 0.5-90 percent, by weight of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compounnd is present in an amount substantially bewteen about 0.000l-l%, preferably 0.0l-l%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures ofa conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 00001-9570, and preferably 0.01-95 percent, by weight of the mixture.

In the case of seed treatment, generally, the active compound is used in 'anamount of substantially between about 0.0l-l0g, andpreferably between about 0.5-5g, per kg of seed.

For soil treatment, generally, the active compound is used in an amount of substantially between about 1-500 g, and preferably between about -200 g, per cubic meter of soil.

The active compound can also be used in accordance with the well-known ultra'low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e., mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufficient. [n this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from aboutto about 95 percent by weight of the active compound or even the l00 percent active substance alone, e.g. about 20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, and more particularly fungi, bacteria, arthropods, e.g., insects and acarids, as well as the corresponding arthropod egg stages, and the like, especially fungi and bacteria, which comprise applying to such pests, i.e. at least one of correspondingly (a) such fungi, (b) such bacteria, (c) such arthropods, (d) such arthropod egg stages, and (e) the corresponding habitat thereof, i.e. the locus to be protected, a pesticidally, i.e. a correspondingly fungicidally, bactericidally, arthropodicidally, e.g. insecticidally and acaricidally, or ovicidally,'effective or toxic amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, fumigating, scattering, dusting, watering. squirting, sprinkling, pouring, dressing, e.g. dry dressing. via incrustation, and the like.

it will be realized, of course. that in connection with the fungicidal, bactericidal, insecticidal, acaricidal and ovicidal use of the instant compounds, the concentration of the particular active compound utilized, above or in admixture with the carrier vehicle. will depend upon the intended application, as the artisan will appreciate. and may be varied within a fairly wide range depending upon the weather conditions and the purpose for which the compound is used. Therefore, in special cases, it is possible to go above or below the aforementioned concentration ranges and amounts per unit weight and volume.

The fungicidal effectiveness as well as the antibacterial effectiveness of the particular compounds of the present invention are illustrated, without limitation, by the following Examples:

EXAMPLE 1 Piricularia and Pellicularia tests Solvent: Dispcrsing agent: Water:

Other additive:

4 parts by .weight acetone 0.05 part by weight sodium oleate 95.75 parts by weight 0.2 part by weight gelatin quired for the desired final concentration of such active compound in the spray liquor is mixed with the stated amount ofsolvent, and the resulting concentrate is then diluted with the stated amount of water containing the stated dispersing agent and other additive.

2 batches, each consisting of 30 rice plants about 2-4 weeks old, are sprayed with the given spray liquor until dripping wet. The plants remain in a greenhouse at temperatures of 22 to 24C and a relative atmospheric humidity of about 70 percent until they are dry. One batch of the plants is then inoculated with an aqueous suspension of 100,000 to 200,000 spores/ml of Piricu- [aria oryzae and placed in a chamber kept at 24 to 26C and 100 percent relative atmospheric humidity. The other batch of the plants is infected with a culture of Pellicularia .rasakii grown on malt agar and placed in a chamber kept at 28 to 30C and 100 percent atmospheric humidity.

5 to 8 days after inoculation, the infestation of all the leaves present at the time of inoculation with Piricu- [aria oryzae is determined as a percentage of the untreated but also inoculated control plants. in the case ofthe plants infected with Pelliculuriu sasukii, the infestation on the leaf sheaths after the same time is also determined in proportion to the untreated but infected control plants. 0 percent means no infestation; whereas 100 percent means that the infestation is exactly as great as in the case of the control plants. ii. Additional test/curative fungicidal action In order to ascertain the curative fungicidal action, the above test (i) is repeated, except that the given active compound is applied not before, but only 16 hours after. inoculation.

The particular active compounds tested, their concentrations, and the results obtained for tests (i) and (ii) can be seen from the following Table l.

TABLE 1 Pi'rieularia (a) and Pellieularia (b) test Infestation as a percentage of the infestation of the untreated control with a concentration of active compound (in percent) 0 Active compound N 0. (sea Ex. 12-18) 0.05 0.025 0.05 0. 025

(A) 0 Pt. 25 100 Our. 100

i N -S()(ll:r

(known) (31) Pr. 0 o 0 17 Our. 0 0

(51) Pr. 0 0 0 29 Cur. 0 50 (14) Pt. 0 0 0 0 Our. 0 0

(21) P1. 0 0 0 (4 A P1. 0 0

NOTE .-Pr. =protective; Cur. =eurative.

EXAMPLE 2 Mycelium growth test Nutrient medium used: 20 parts by weight agar-agar 30 parts by weight malt extract 950 parts by weight distilled water Proportion of solvent to nutrient medium: 2 parts by weight acetone 100 partsby weight agar nutrient medium The amount of the particular active compound re quired for the desired final concentration ofsuch active compound in the nutrient medium is mixed with the stated amount of solvent. The resulting concentrate is then thoroughly mixed, in the stated proportion, with the liquid nutrient medium (which has been cooled to 42C) and is thereafter poured into'Petri dishes of9 cm diameter. Control dishes to which the active compound preparation has not been added are also set up.

When the nutrient medium has cooled and solidified, the dishes are inoculated with the species of fungi stated in the Table below and incubated at about 21C. Evaluation is carried out after 4-l0 days, dependent upon the rate of growth of the fungi. When evaluation is carried out the radial growth of the mycelium on the treated nutrient media is compared with the growth on the control nutrient media. In the evaluation of the fungus growth, the following characteristic values are used:

0 no fungus growth 1 very strong inhibition of growth 2 medium inhibition of growth 3 slight inhibition of growth 4 growth equal to that of untreated control.

The particular active compounds tested, their concentrations, and the results obtained can be seen from the following Table 2.

Table 2 Mzcelium growth test Active compound Concentration of Fungi No. (see But. 12-18) active compound in ppm II II a 3 18 g bi u t: u a g v p a. u o o m u .4 g H 33 a u 3 I; g. :1 H a O 5 8 U U N 5 U 0 U U in U 0 U H 1: v4): h O O I O U Q P. $4 *1 O 4 vi N In 4) L4 Q. H 8 H H U N G U P U U U O H g I! ll! N U Q O *4 a "a as 2.. a? 2'; a: :2: 713 5.71 9- 8 a e an: a. o u. u m n a .a

Untreated control 4 4 o 6 4 4 4 (3 10 o 0 v o o 10 o o 2 o o o 1 1'0 0 o o o 0 o a c o o EXAMPLE 3 EXAMPLE 4 Bacteria test/Xanthomonas oryzae Seed dressing test/bunt of wheat (seed-borne mycosis) S l 4 b h w To produce a suitable dry dressing, the particular aco vent: parts y welg t acetone a a I Dispersing agent: 0.05 part by weight sodium oleate [we compou'nd extended wllth '1 mlxwre of s' Watt-r; 95.75 parts by weight parts by weight of talc and kieselguhr to provide a Other additive: 0.2 part by weight gelatin I The amount of the particular active compound required for the desired final concentration of such active compound in the spray liquor is mixed with the stated amount of solvent, and the resulting concentrate is then diluted with the stated amount of water containing the stated dispersing agent and other additive.

rice plants about 30 days old are sprayed with the given spray liquor until dripping wet..The plants remain in a greenhouse at temperature of 22 to 24C and a relative atmospheric humidity of about 70 percent until they are dry. Needles are then dipped into an aqueous bacteria suspension of Xantlmmunas oryzae and the plants are inoculated by pricking the leaves. After inoculation, the plants are placed in a chamber kept at 26 to 28C and 80 percent relative atmospheric humidity.

10 days after inoculation, the infestation in the case of all the inoculated leaves injured by pricks and previously treated with the given active compound preparation is determined as a percentage of the untreated but also inoculated leaves of the control plants. 0 percent means that there is no infestation; whereas 100 percent means that the infestation is exactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations, and the results obtained can be seen from the following Table 3.

Table 3 Bacteria test/Xanthomonas oryzae Active compound No. lnfestation as a percentage of (see Ex. l2 l8) the infestation of the untreated control with a concentration of active compound (in 71) of finely powdered mixture with the desired final concentration of such active compound.

Wheat seed is contaminated with 5 g of the chlamydospores of Tilleriu Caries per kg of seed. To apply the given dressing, the seed is shaken with such dressing in a closed glass flask. The seed, on moist loam under a cover ofa layer of muslin and 2 cm of moderately moist compost soil, is exposed to optimum germination conditions for the spores for 10 days at l0C in a refrigerator.

The germination of the spores on the wheat grains, each of which is contaminated with about 100,000 spores, is subsequently determined microscopically. The smaller the number of spores which have germinated, the more effective is the given active compound.

The particular active compounds tested, their concentrations in the dressing, the amounts of dressing used and the percentage spore germination obtained can be seen from the following Table 4.

Table 4 Seed dressing test/hunt of wheat Active Amount 01' compound No. Concentration of dressing Spore (see Ex. l2-l8) active compound applied in gerin 71 by weight g/kg seed mination undressed 10 (3,) 30 I 0.000 10 I 0.005 (5 30 1 0.000 10 I 0.005 (1 30 I 0.000 10 I 0.005 (2:1) 30 I 0.000

EXAM PLE 5 Phytophthora test Solvent: Dispersing agent:

Water: 950 parts by weight hours at 20C and at a relative atmospheric humidity of 70 percent. The tomato plants are then inoculated with -an aqueous spore suspension of Phymphrlmra infesrans.

The plants are then brought into a moist chamber kept at an atmospheric humidity of l% and a temperature of l820C.

After days the infestation of the tomato plants is determined as a percentage of the untreated but also inoculated control plants. 0 percent means no-infestation; whereas 100 percent means that the infestation is exactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations, and the results obtained can be seen from the following Table 5.

TABLE 5 Phytophthora test Infestation as a percentage of the infestation of the untreated control with a concentration of active Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 part by weight alkylaryl polyglycol ether Water: 95.0 parts by weight The amount of the particular active compound required for the desired final concentration in the spray liquid is mixed with the stated amount of solvent, and the resulting concentrate is then diluted with the stated amount of water containing the stated emulsifier.

Young cucumber plants (Delikatess variety) with about three foliage leaves are sprayed with the given spray liquid until dripping wet. The cucumber plants remain in a greenhouse for 24 hours to dry. Such plants are then, for the purpose of inoculation, dusted with conidia of the fungus Erysiphe polyp/raga. The plants are subsequently placed in a greenhouse kept at 23- 24C and at a relative atmospheric humidity of about 75 percent.

After l2 days, the infestation of the cucumber plants is determined as a percentage of the untreated but also inoculated control plants. percent means no infestation; whereas 100 percent that the infestation is exactly as great as in the case of the control plants.

The particular active compounds tested, their con centrations, and the results obtained can be seen from the following Table 6.

TABLE 0 Erysiphe test Infestation as a percentage of the infestation of the untreated control with a concentration of active compound (in percent) Active compound No. (see Ex. 12-18) 0.0031 0.00150 )l NSC 01:

(known) EXAMPLE 7 Fusicladium test (apple scab) [Protective] Solvent: 4.7 parts by weight acetone Emulsifier: 0.3 part by weight alkylaryl polyglycol other Water: 95.0 parts by weight stated emulsifier.-

Young apple seedlings in the 4-6 leaf stage are sprayed with the given spray liquid until dripping wet.

The plants remain in agreenhousefQr il hours at 20C and at a relative atmospheric humidity of percent. Such plants are then inoculated with an aqueous conidium suspension of the apple scab causative organism (Fusicladium dendrilicum and incubated for 18 hours in a humidity chamber kept at l820C and at a relative atmospheric humidity of l00 percent.

The plants are then again placed in a greenhouse for 14 days.

15 days after inoculation; the infestation ofthe seed- I lings is determined as a percentage of the untreated but also inoculated control plants. 0 percent means no infestation; whereas percent means that the infestation is exactly as great as in the case of the control plants. I

The particulr active compounds tested, their concentrations, and the results obtained can be seen from the following Table 7.

15 M 16 1 usicladiil t e s t (p rotoctive) EXAMPLE 9 Infestation as a percentage Fusicladium test (apple scab) [Curative] ol the infestation of the untreated control with a Solvent: 4.7 parts by weight acetone concentration of activfl 5 Emulsifier: 0.3 part by weight alkylaryl polyglycol other g L l (in percent) Water: 95.0 parts by weight Active compound No. (sue Ex. 12-18) 0.00156 0.00030 The amount of the particular active Compound (A) 32 77 quired for the desired final concentration of such active compound in the spray liquid is mixed with the stated amount of solvent, and the resulting concentrate is then diluted with the stated amount of water containing the stated emulsifier.

Young apple seedlings in the 4-6 leaf stage are inoculated with an aqueous conidium suspension of the apple scab causative organism Fusicladium dendriticum 5 3g .'and incubated for 18 hours in a humidity chamber kept at l8-20C and at an atmospheric humidity of 100 percent. The plants are then placed in a greenv. 20 house where they dry.

EXAMPLE 8 After standing for a suitable period oftime, the plants Podosphaera test (powdery mildew of apples) [Protecare p y l dripping wet h the give" Spray five] liquid prepared m the manner described above. The

I b ht-acewne plants are then agaln placed in a greenhouse. er: 8:; ggfi z'fi amylmyl polygly'cfl ether I5 days after Inoculation, the lnfestatlon of the apple Water: 95.0 parts by weight seedlings is determined as a percentage of the un- The amount of the particular active compound treated but also inoculated control plants. 0 percent quired for the desired final concentration of such active l "l i whereas I00 Mal-cent means Compound in the spray liquid is mixed with the Stated the Infestation is exactly as great as In the case of the amount of solvent, and the resulting concentrate is then control a diluted with the stated amount of water containing the T Part'cular W cqmpmmds Stated emulsifimn I I centratlons, the perlod of time between lnoculatlon and Young apple seedlings in the leaf stage are spraying and the results obtained can be seen from the sprayed with the given spray liquid until dripping wet. I followmg Table Table The plants remain in a greenhouse for 24 hours at 20C TABLE 9 and at a relative atmospheric humidity of 70 percent. Fusicladiumtest (curative) Such plants are-then inoculated by dusting with conidia Infestation as a pemm of the apple powder mildew causative organism Podusplmera leucorricha Salm.) and placed in a greenhouse with aconoentration kept at a temperature of 2 l -23C and at a relative at- 40 d ififie' i n iii clifiii' mospheric humidity of about 70 percent. I Period Ten y after inoculation, the infestation of tha Active compound N0. (see Ex. 12-18) in hours 0.0125 0.0062 seedlings is determined as a percentage of the un- 42 treated but also inoculated control plants. 0 percent means no infestation; whereas 100 percent means that 45 NTSTCCI the infestation is exactly as great as in the'case of the control plants.

The particular active compounds tested, their concentrations, and the results obtained can be seen from 42 1 9 the following Table 8. v t; 2 5S rfi'fiijl js" Podosphaera Test (protective) EXAMPLE l0 teatassistant: Erysiphe test 33 32322268: 33 Solvent: 4.7 parts by weight acetone compound (in percents Emulsifier: 0.3 part by weight alkylaryl polyglycol ether Water: 95.0 parts by weight Active compound No. (see Ex. 12-18 0.00039 0. 00010 The amount of the particular active compound re- 0 100 100 quired for the desired final concentration in the treat- 0 mentliquid is mixed with the stated amount of the solvent, and the resulting concentrate is then diluted with I sc on the stated amount of water containing the stated emulsifler. v y H Young cucumber plants, in the one to two-leaf stage, 0 grown in standard soil are watered within a week with (kmwm 20 cc of the treatment liquid in the stated active comglg l 1 pound concentration with reference to cc of soil,

i.e. by pouring the treatment'liquid onto the plants and viscinal soil. The plants thus treated are, after treatment. inoculated with conidia of the fungus Erysiplie cic/mrac'eum. The plants are then placed in a greenhouse kept at 23-24C and at a relative atmospheric humidity of 70 percent.

After 12 days, the infestation of the cucumber plants is determined as a percentage of the untreated but also inoculated control plants. percent means no infestation; whereas I00 percent means that the infestation is exactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations. and the results obtained can be seen from the following Table I0.

Table I0 Erysiphe test (systemic) Active compound No. Infestation as a percentage of 0.3 part by weight alkylaryl polyglyeol ether 950 parts by weight Dispcrsing agent:

Water:

The amount of the particular active compound required for the desired final concentration of such active compound in the treatment liquid is mixed with the stated amount of solvent, and the resulting concentrate is then diluted with the stated amount of water containing the stated dispersing agent.

Young apple seedlings; in the 3-4 leaf stage. grown in standard soil are watered once within a week with 20 cc of the treatment liquid in the stated active compound concentration with reference to 100 cc of soil, i.e. by pouring the treatment liquid onto the plants and viscinal soil. The plants thus treated are, after treatment, inoculated with an aqueous conidium suspension of Fusicludium dentricum and incubated for 18 hours in a humidity chamber kept at l8-20C and at a relative atmospheric humidity of I00 percent. The plants are then again place in a greenhouse for l4 days.

days after inoculation, the infestation of the seedlings is determined as a percentage of the untreated but also inoculated control plants. 0 percent means no infestation; whereas 100 percent means that the infestation is exactly as great as in the case of the control plants.

The particular active compounds tested, their concentrations and the results obtained can be seen from the following Table 11.

Table l l (i) 10 g (0.045 mol) w-isocyanato-dodecanoic acid nitrile and 10 ml acetone are added to 7.7 g (0.0376 mol) N-(benzimidazol-Z-yl)-carbamic acid ethyl ether, 30'

ml of dry acetone and 0.] ml picoline, and stirred at 40C for 2 hours. After standing for l8 hours at 23C, the reaction mixture is diluted with 40 ml acetone. The resulting crystals are separated and washed with ligroin. Such crystals, unlike N(benzimida2ol-2 yl)- carbamic acid ethyl ester, are completely soluble in methylene chloride thus indicating that all N- 9benzimidazol-2-yl)carbamic ethyl ester has been reacted. The crystals of the desired product are dried at 40C/C.l mm Hg. Yield 13.5 g of 2-ethoxy-carbonylamino-3-(w-cyano-undecyl)-carbamyl-benzimidazole.

Analysis:

Calculated: 16.3771 H.237 Found: 16.2% ll.5%

The infra-red spectrum of the compound in KBr shows an NYH groups, the proton of which stands in a hydrogen bridge bond, through a broad absorption band at 32000 cm, the -(CH). group at 2920 cm and at 715 cm"; the C=O group of the cyano-undecylcarbamyl substituent at l7l0 cm, and the nitrile group at 2240 cm. In the spectrum, no- N =C=O band is indicated.

Preparation of the N-(benzimidazol-Z-yl)-carbamic acid ethyl ester used as starting material (ii) 302 g (2.78 mols) chloroformic acid ethyl ester are added to 2 mols of S-benzyl-isothiourea hydrochloride in 800 ml of water and 200 ml acetonitrile. 25 percent solution of sodium hydroxide is added dropwise so rapidly that, with external cooling, a temperature of +25C is not exceeded, and the solution of sodium hydroxide is added for as long as the pH value does notrise above 8. Stirring is effected for-a further minutes during which control of the pH value is continued. If necessary, a little more solution of sodium hydroxide is.

added. 1.5 liters of water are added to the two-phase mixture and the aqueous phase is separated. 0.5 liter of water, 216 g (2 mols) o-phenylene-diamine as well as g acetic acid are added to the heavy organic phase 1 which contains N -ethoxy-carbonyl-2-(S-benzyl)isothiourea and N, N -bis-9ethoxy-carbonyl)-2-(S-benzyl)-isothi ourea. and the mixture is heated, with stirring. to 80-90C in 15 minutes. It is kept at this temperature for 2 hours. After cooling, the aqueous phase is separated, and the paste-like reaction product is stirred with water and then with isopropyl alcohol, after which the crystals formed are filtered off with suction. The crystals are washed with isopropyl alcohol and with water and dried in a vacuum. 335 g- N- (benzimidazol-Z-yl)-carbamic acid ethyl ester are obhours at 120C. After brief blowing out ofthe reaction mixture with nitrogen, distillation is effected. Yield 42.5 g of l07-isocyanato-dodecanoic acid nitrile (b.p.. l24-l26.5C/0.l mm Hg).

EXAMPLE l3 [reaction variant(a)] (i) 38 g (0.199 mol) N-(benzimidazol-2-yl)- carbamic acid methyl ester, 80 ml methylene chloride, 1 ml picoline, and 30 g (0.218 mol) -isocyanatocaproic acid nitrile, are kept at 40C for 3.5 hours. The reaction product is dissolved out by addition of 300 ml methylene chloride. Filtration from the undissolved N- (benzimidazol-Z-yl) carbamic acid methylester starting material is effected. 200 ml benzine are added to the filtrate and the methylene chloride is evaporated in a waterjet vacuum; crystals separate. These crystals are filtered off with suction and washed with a little water and dried at 40C/0.] mm Hg. Yield 58.5 g of 2- methoxy-carbonylamino-3-(w-cyano-pentyU-carbamyl-benzimidazole.

Analysis: N

Calculated: 21.26% l4.57% Found: 2l.2 14.5

1,524,675) 2.2 liters acetonitrile, 1.] liters of water and 734 g (7.77 mols) chloroformic acid methyl ester, are provided. 25 percent solution of sodium hydroxide is,

with external cooling, run in so rapidly that the temperature does not exceed +25C and in such amount that the pH value of 8 is not exceeded. Stirring is effected for 30 minutes, with continued control of the pH value. N N?-bis-(methoxy-carbonyl)-S-(2,4-diisopropyltion. With the aid of an immersion filter, the liquid phase is suction filtered as far as possible, and washing is effected with about liters of water, 395 g (3.66 mols) o-phenylene-diamine, 330 g acetic acid and 2.8 liters of water, are then added to the reaction vessel,'and heating to 8090C is effected for 100 minutes. After cooling, the liquid phase is drawn off, and the pasty reaction product is washed once with water and then with isopropyl alcohol,

whereupon crystals are precipitated. The crystals sspatats w h d. w ppro yl al q a with water, and then dried in a vacuum. Yield 582 of N-(benzimidazol-2-yl)-carbamic acid methyl ester. From the isopropyl-alcohol-containing wash liquor, 480 g 2,4-diisopropyl-benzylmercaptan of boiling point -73C/0.08 mm Hg can be obtained by distillation. Instead of 2, 4-diisopropyl-benzyl-isothiourea hydrochloride, 2, 5-diisopropyl-benzyl-isothiourea hydrochloride can also be used, 2,5-diisopropyl-benzylmercaptan of boiling point 8 8C/0.ll mm Hg being obtained as by-product.

EXAMPLE 14 [reaction variant (a)] C ONH(CH1)5ON s'r CNH-COO-C2Hs \N 14) 25 g w-isocyanato-caproic acid nitrile are added to 31.8 g N-(benzimidazol-Z-yl)-carbamic acid ethyl ester, 17 g picoline,-and 250 ml dimethyl formamide, and kept at 60C for 3 hours. The solution is filtered and, after standing for 16 hours at room temperature, diluted with 2 liters of water. The crystals formed are separated, washed with water and with 50 percent aqueous acetonitrile, and dried at 60C/0.1 mm Hg. Yield 46.5 g of 2-ethoxy-carbonylamino-3-( l07-cyano-pentyl)- carbamyl-benzimidazole.

Analysis: N 0

Calculated: 20.4% 13.98% Found: 20.5% l4.2 74

The infra-red spectrum of the compound in KBr shows a strongly associated N-H group at 3200 cm,

'the -(CH group at 2930 cm and at 720 cm", the

nitrile group at 2240 cm and the C=O group of the cyano-pentyl-carbamyl substituent at 1715 cm- EXAMPLE l5 [reaction variant (a)] (I]ONH(CH2)5CN EXAMPLE 16 [reaction variant (a)] Analogous to the procedure of Examples 12-14,

there is obtained 2-propionyl-amino-3-( w-cyano-pentyl )-carbamylbenzimidazole Analysis: N

Calculated: Found:

The infra-red spectrum of the compound in KBr shows a strongly associated N-H band at 3200 cm", the (CH group at 2935 cmand at 725 cm, the nitrile group at 2240 cm and the C=O- group of the w-cyano-pentyl-carbamyl substituent at 1710 cm"- EXAMPLE 1? [reaction variant (a OO -NH- G HQM- CN i Analysis: N 0

Calculated: 25.85% 5.90% Found: 25.9 6.17%

The infra-red spectrum of the compound in KBr shows the N-H group as double band at 3418 cm", the (CH group at 2930 cm", the nitrile group at 2245 cm", and the C=O group of the w-cyano-pentylcarbamyl substituent as a shoulder band at 1705 cm". An O=C=N group is not evidenced in the spectrum.

EXAMPLE l8 28 g (0.203 mol) w-isocyanato-ca'proic acid. nitrile are added to 29.4 g (0.2 mol) 2-amino-5-methylbenzimidazole and 250 ml methylene chloride, at -15C. Stirring is effected at 0C for about minutes. and then the temperature is allowed to rise and is kept at room temperature for 24 hours. The resulting crystals areseparated at 0C, washed with 150 ml methylene chloride and then with water. Yield 52 g of 2 -amino-3-(Q-cyano-pentyl)-carbamyl-6-methylbenzimidazole; m.p. C (decomp.).

Analysis: N 0

Calculated: 24.54% 5.61% Found: 242 "/1 5.66%

The infra-red spectrum of the compound in KBr .shows the N-H group at 3430 cm" and at 1608 cm,

the -(CH group at 2940 cm and at 705 cm", the nitrile group at 2240 cm1,'and the C=O group of the W-cyano-pentyl-carbamyl substituent as a shoulder band at 1705 cm". An O=C=N group is not evidenced in the spectrum.

It will be realized by the artisan that all of the foregoing compounds contemplated by the present invention possess the desired strong fungicidal, bactericidal, arthropodicidal, i.e.' insecticidal and acaricidal, and ovicidal properties, with regard to a broad spectrum of activity, as well as a comparatively low toxicity toward warm-blooded creatures and a concomitantly low phytotoxicity withrespect to higher plants, enabling such compounds to be used with correspondingly favorable compatibility with respect to warm-blooded creatures and higher plants for more effective control and/or elimination of fungi, bacteria, arthropods and/or arthropod egg stages, by selective application of such compounds to such fungi, bacteria, arthropods, arthropod egg stages and/or their habitat.

It 'will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. A method of combating insects, acarids, insect ova or acarid ova which comprises applying to (a) said insects, (b) said acarids, (c) said insect ova, (d) said acarid ova or (e) the corresponding habitats thereof, an insecticidally, acaricidally, or ovicidally effective amount of a N-(w-cyano-alkyl)-carbamylbenzimidazole of the formula Co-NE-wHJJ-dty in which R is selected from the group consisting of hydrogen, alkoxycarbonyl of 2-5 carbon atoms and alkylcarbonyl of 15 carbon atoms, R is selected from the carbon atoms, R is selected from the group consisting 5 of hydrogen and methyl, and x is 5-11.

4. The method of claim 1, wherein the compound is 2-ethoxy-carbonylamino-3-(w-cyano-pentyU-carbamyl-benzimidazole of the formula 5. The method of claim 1, wherein the compound is- Z-ethoxy-carbonylamino-3-( w-cyano-undecyl carbamylbenzimidazole of the'formula 6. The method of claim 1, wherein the compound is 2-methoxy-carbonylamino-3-(w-cyano-pentyU-carbamyl-benzimidazole of the formula 7. The method of claim 1, wherein the compound is '2 -methoxy-carbonylamino 3- m-cyano-pentyl carbamyl-5 methyl penzimidazole of the formula |C O-NH{ cum- N 8. The method of claim 1, wherein the compound is 2-methoxy-carbonylaminoJ-(w-cyano-pentyl)- carbamyl-6-methylbenzimidazole of the formula 9. The method of claim 1, wherein the compound is 2-propionyl-amino-3-( w-cyano-pentyl )-carbamylbenzimidazole of the formula ([JO-NI-I-(CI-ifis-C N /N \CNH-COC2H5 10. The method of claim 1, wherein the compoundis l-(w-cyano-pentyl)-carbamyl-2-aminobenzirnidaz ole ofthe formula 11. The method ofclaim I. wherein the compound is Z-amino-3-(w-cyano-pentyl)-carbumyl-6-methylbenzimidazole of the formula UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 864,490 Dated February 4 1975 Inventofls) (P g 2 of It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

C01. 22, line 8 cancel "1L and substitute w Col. 22 liue 2O cancel "w" aud substitute Col. 22, claim 2, line 4, after "atoms" insert Signed and sealcdwhis eleventh Of N0vemberl975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN l i g ffifl'" ('mnmissimwr vj'lurents um] 'I'rmlcmurkx 

1. A METHOD OF COMBATING INSECTS, ACARIDS, INSECT OVA OR ACARID OVA WHICH COMPRISES APPLYING TO 9A) SAID INSECTS 9B) SAID ACARIDS, (C) SAID INSECT OVA, (D) SAID ACARID OVA OR (E) THE CORRESPONDING HABITATS THEREOF, AN INSECTICIDALLY, ACARICIDALLY, OR OVICIDALLY EFFECTIVE AMOUNT OF A N-(W-CYANO-ALKYL)CARBAMYL-BENZIMIDAZOLE OF THE FORMULA
 2. The method according to claim 1, wherein R is selected from the group consisting of hydrogen, alkoxycarbonyl of 2-4 carbon atoms and alkyl-carbonyl of 2-4 carbon atoms R'' is selected from the group consisting of hydrogen and alkyl of 1-3 carbon atoms, and x is 5-11.
 3. The method according to claim 1, wherein R is selected from the group consisting of hydrogen, alkoxy-carbonyl of 2-3carbon atoms and alkylcarbonyl of 2-3 carbon atoms, R'' is selected from the group consisting of hydrogen and methyl, and x is 5-11.
 4. The method of claim 1, wherein the compound is 2-ethoxy-carbonylamino-3-( omega -cyano-pentyl)-carbamyl-benzimidazole of the formula
 5. The method of claim 1, wherein the compound is 2-ethoxy-carbonylamino-3-( omega -cyano-undecyl)-carbamylbenzimidazole of the formula
 6. The method of claim 1, wherein the compound is 2-methoxy-carbonylamino-3-( omega -cyano-pentyl)-carbamyl-benzimidazole of the formula
 7. The method of claim 1, wherein the compound is 2-methoxy-carbonylamino-3-( omega -cyano-pentyl)-carbamyl-5-methyl-benzimidazole of the formula 155/6
 8. The method of claim 1, wherein the compound is 2-methoxy-carbonylamino-3-( omega -cyano-pentyl)-carbamyl-6-methylbenzimidazole of the formula
 9. The method of claim 1, wherein the compound is 2-propionyl-amino-3-( omega -cyano-pentyl)-carbamyl-benzimidazole of the formula
 10. The method of claim 1, wherein the compound is 1-( omega -cyano-pentyl)-carbamyl-2-amino-benzimidazole of the formula
 11. The method of claim 1, wherein the compound is 2-amino-3-( omega -cyano-pentyl)-carbamyl-6-methyl-benzimidazole of the formula 